Safening 6-(trisubstituted phenyl)-4-amino-2-pyridinecarboxylate herbicide injury on cereal crops

ABSTRACT

Herbicidal injury caused by 6-(trisubstituted phenyl)-4-amino-2-pyridinecarboxylates in wheat and barley is reduced with the use of AD67 (MON 4660), benoxacor, 2-CBSU, daimuron, dichlormid, dicyclonon (BAS 145 138H), fenchlorazole-ethyl, fenclorim, fluxofenim, furilazole (MON 13900), glyphosate, isoxadifen-ethyl, mefenpyr-diethyl, naphthalic anhydride, oxabetrinil and mixtures thereof.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. patentapplication Ser. No. 12/620,869, filed Nov. 18, 2009, which claimspriority to U.S. Provisional Application Ser. No. 61/117,332 filed Nov.24, 2008, the disclosures of which are expressly incorporated herein byreference.

FIELD OF THE INVENTION

This invention concerns the safening of the herbicidal injury caused by6-(trisubstituted phenyl)-4-amino-2-pyridinecarboxylates in cerealcrops.

BACKGROUND OF THE INVENTION

When agrochemicals, such as plant protection agents and especiallyherbicides, are used, the cultivated plants may be damaged to a certaindegree, depending on factors such as the dose of agrochemicals and theirmethod of application, the species of cultivated plant, the nature ofthe soil and climatic conditions, for example, length of time ofexposure to light, temperature and amounts of precipitation. Thus, it isknown that cultivated plants which are to be protected from the adverseeffect of undesirable plant growth may be damaged to a certain degreewhen an effective dose of herbicide is used. Various substances whichare capable of specifically preventing the adverse effect of anherbicide on the cultivated plants, i.e. of protecting the cultivatedplants without at the same time noticeably influencing the herbicidalaction on weeds to be combated, have been proposed to solve thisproblem. However, it has been found that the antidotes proposedfrequently have only a narrow field of use, i.e., a particular antidoteis frequently suitable only for use with individual species ofcultivated plants and/or for protecting the cultivated plants fromindividual herbicidal substances or classes of substances.

U.S. Pat. No. 7,314,849 B2 describes certain 6-(polysubstitutedaryl)-4-amino-2-pyridinecarboxylate compounds and their use asherbicides. While certain of these compounds have been shown to beparticularly effective herbicides for controlling undesirable vegetationin cereal crops, they have also been shown to produce slight amounts ofdamage to both wheat and barley at concentrations required to adequatelycontrol the undesirable vegetation.

SUMMARY OF THE INVENTION

It has now been found that, surprisingly, the phytotoxic effect ofcertain 6-(poly-substituted aryl)-4-amino-2-pyridinecarboxylatecompounds, which have an auxinic mode of action, on wheat and barley canbe ameliorated by the use of certain safeners. The present inventionconcerns a method of protecting cereal crops from the harmful effects ofa 6-(trisubstituted phenyl)-4-amino-2-pyridinecarboxylate herbicide ofthe formula (I)

-   -   wherein hal represents F, Cl or Br, and R represents methyl or        ethyl,        and its agriculturally acceptable salt, ester and amide        derivatives which comprises contacting wheat and barley with, or        applying to the area under cultivation, a safener, or a        compatible herbicide capable of safening, selected from the        group consisting of AD67 (MON 4660), benoxacor, 2-CBSU,        daimuron, dichlormid, dicyclonon (BAS 145 138H),        fenchlorazole-ethyl, fenclorim, fluxofenim, furilazole (MON        13900), glyphosate, isoxadifen-ethyl, mefenpyr-diethyl,        naphthalic anhydride, oxabetrinil and mixtures thereof.

The present invention also concerns a composition for protecting wheatand barley from the harmful effects of a 6-(trisubstitutedphenyl)-4-amino-2-pyridinecarboxylate herbicide of the formula (I)

-   -   wherein hal represents F, Cl or Br, and R represents methyl or        ethyl,        and its agriculturally acceptable salt, ester and amide        derivatives which comprises, in addition to the        6-(trisubstituted phenyl)-4-amino-2-pyridinecarboxylate        herbicide, a safener or compatible herbicide capable of safening        selected from the group consisting of AD67 (MON4660), benoxacor,        2-CBSU, daimuron, dichlormid, dicyclonon (BAS 145 138H),        fenchlorazole-ethyl, fenclorim, fluxofenim, furilazole (MON        13900), glyphosate, isoxadifen-ethyl, mefenpyr-diethyl,        naphthalic anhydride, oxabetrinil, and mixtures thereof. In        preferred compositions, the 6-(trisubstituted        phenyl)-4-amino-2-pyridinecarboxylate herbicide is a        4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylic        acid derivative or a        4-amino-3-chloro-6-(2,4-dichloro-3-methoxyphenyl)-2-pyridinecarboxylic        acid derivative.

It has been surprisingly found that the use of a spirooxazolidinesafener such as AD 67 (MON 4660) in composition with apyridinecarboxylate herbicide of the formula (I) exhibits a protectingeffect against the phytotoxicity of the pyridinecarboxylate herbicide offormula (I) on wheat (Triticum aestivum L; TRZAS) and barley (Hordeumvulgare L; HORVS) without losing the herbicidal effects on weeds such ascleavers (Galium aparine L; GALAP), purple deadnettle (Lamium purpureumL; LAMPU), corn poppy (Papaver rhoeas L; PAPRH).

The combinations of dichloroacetamide safeners such as benoxacor,dichlormid, dicyclonon (BAS 145 138H), furilazole (MON 13900) and apyridinecarboxylate herbicide of formula (I) resulted in an unexpectedsafening effect against the phytotoxicity of the pyridinecarboxylateherbicide of formula (I) on wheat (Triticum aestivum L; TRZAS) andbarley (Hordeum vulgare L; HORVS) without reduction of the herbicidaleffects on weeds such as cleavers (Galium aparine L; GALAP), purpledeadnettle (Lamium purpureum L; LAMPU), corn poppy (Papaver rhoeas L;PAPRH), chickweed (Stellaria media L; STEME), bird's-eye speedwell(Veronica persica L; VERPE).

It has also been surprisingly found that a mixture of abenzenesulfonamide safener such as 2-CBSU and a pyridinecarboxylateherbicide of formula (I) exhibits a safening effect against thephytotoxicity of the pyridinecarboxylate herbicide of formula (I) onwheat (Triticum aestivum L; TRZAS) and barley (Hordeum vulgare L; HORVS)without losing the herbicidal effects on weeds such as cleavers (Galiumaparine L; GALAP), purple deadnettle (Lamium purpureum L; LAMPU), cornpoppy (Papaver rhoeas L; PAPRH).

It has also been unexpectedly found that the mixture of phenyl pyrazolesafeners such as fenchlorazole-ethyl, mefenpyr-diethyl and apyridinecarboxylate herbicide of formula (I) shows a safening effectagainst the phytotoxicity of the pyridinecarboxylate herbicide offormula (I) on wheat (Triticum aestivum L; TRZAS) and barley (Hordeumvulgare L; HORVS) without reducing the herbicidal effects on weeds suchas cleavers (Galium aparine L; GALAP), purple deadnettle (Lamiumpurpureum L; LAMPU), corn poppy (Papaver rhoeas L; PAPRH), bird's-eyespeedwell (Veronica persica L; VERPE), Russian thistle (Salsola ibericaL; SASKR), wild pansy (Viola tricolor L; VIOTR).

The combination of a phenylpyrimidine safener such as fenclorim and apyridinecarboxylate herbicide of formula (I) exhibits a safening effectagainst the phytotoxicity of the pyridinecarboxylate herbicide offormula (I) on wheat (Triticum aestivum L; TRZAS) and barley (Hordeumvulgare L; HORVS) without losing the herbicidal effects on weeds such ascleavers (Galium aparine L; GALAP), purple deadnettle (Lamium purpureumL; LAMPU), corn poppy (Papaver rhoeas L; PAPRH), wild buckwheat(Polygonum convolvulus L; POLCO).

The combinations of safeners of the oxime class such as fluxofenim,oxabetrinil and a pyridinecarboxylate herbicide of formula (I) haveresulted in an unexpected safening effect against the phytotoxicity ofthe pyridinecarboxylate herbicide of formula (I) on wheat (Triticumaestivum L; TRZAS) and barley (Hordeum vulgare L; HORVS) withoutreduction of the herbicidal effects on weeds such as cleavers (Galiumaparine L; GALAP), purple deadnettle (Lamium purpureum L; LAMPU), cornpoppy (Papaver rhoeas L; PAPRH), scented mayweed (Matricaria chamomilaL; MATCH), Russian thistle (Salsola iberica L; SASKR).

It has also been surprisingly found that the mixture of oxime ethersafeners, such as isoxadifen-ethyl, and a pyridinecarboxylate herbicideof formula (I) shows a safening effect against the phytotoxicity of thepyridinecarboxylate herbicide of formula (I) on wheat (Triticum aestivumL; TRZAS), durum wheat (Triticum durum L; TRZDU), and barley (Hordeumvulgare L; HORVS) without reducing the herbicidal effects on weeds suchas purple deadnettle (Lamium purpureum L; LAMPU), corn poppy (Papaverrhoeas L; PAPRH).

The mixture of a naphthopyranone safener such as naphthalic anhydrideand a pyridinecarboxylate herbicide of formula (I) shows an unexpectedsafening effect against the phytotoxicity of the pyridinecarboxylateherbicide of formula (I) on wheat (Triticum aestivum L; TRZAS) andbarley (Hordeum vulgare L; HORVS) without reduction of the herbicidaleffects on weeds such as cleavers (Galium aparine L; GALAP), purpledeadnettle (Lamium purpureum L; LAMPU), corn poppy (Papaver rhoeas L;PAPRH), kochia (Kochia scoparia L; KCHSC), wild pansy (Viola tricolor L;VIOTR).

It has also been unexpectedly found that the mixture of apyridinecarboxylate herbicide of formula (I) and a phenylurea herbicidesuch as daimuron exhibits a surprising safening effect against thephytotoxicity of the pyridinecarboxylate herbicide of formula (I) onwheat (Triticum aestivum L; TRZAW), durum wheat (Triticum durum L;TRZDU), and barley (Hordeum vulgare L; HORVS) without reducing theherbicidal effects on weeds such as purple deadnettle (Lamium purpureumL; LAMPU), corn poppy (Papaver rhoeas L; PAPRH).

It has been also surprisingly found that the mixture of apyridinecarboxylate herbicide of the formula (I) and an EPSP(5-enolpyruvylshikimate-3-phosphate) synthase inhibitor herbicide suchas glyphosate exhibits an unexpected safening effect against thephytotoxicity on wheat (Triticum aestivum L; TRZAS) and barley (Hordeumvulgare L; HORVS).

DETAILED DESCRIPTION OF THE INVENTION

The pyridinecarboxylates of formula I are a new class of compoundshaving herbicidal activity. A number of pyridinecarboxylate compoundsare described in U.S. Pat. No. 7,314,849, including4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylicacid (compound 1) and4-amino-3-chloro-6-(2,4-dichloro-3-methoxyphenyl)-pyridine-2-carboxylicacid (compound 2). The pyridinecarboxylates of formula (I) controlannual grass weeds and broadleaf weeds in wheat and barley but are alsophytotoxic to wheat and barley at commercially herbicidal doses.

AD67 (MON 4660) is the common name for4-(dichloroacetyl)-1-oxa-4-azaspiro[4,5]decane. Its safening activity isdescribed in The Pesticide Manual, Thirteenth Edition, 2003. AD67 (MON4660) is used as a safener in maize.

Benoxacor is the common name for(±)-4-(dichloroacetyl)-3,4-dihydro-3-methyl-2H-1,4-benzoxazine. Itssafening activity is described in The Pesticide Manual, FourteenthEdition, 2006. Benoxacor is used as a safener in maize.

2-CBSU is the common name forN-(aminocarbonyl)-2-chlorobenzenesulfonamide. Its safening activity isdescribed in Modern Crop Protection Compounds, 2007. 2-CBSU has beenshown to safen herbicidal injury in maize.

Daimuron is the common name forN-(4-methylphenyl)-N′-(1-methyl-1-phenylethyl)urea. Its herbicidalactivity is described in The Pesticide Manual, Fourteenth Edistion,2006. Daimuron is used as a selective herbicide of cyperaceous weeds andannual grass weeds in paddy rice.

Dichlormid is the common name for N,N-diallyl-2,2-dichloroacetamide. Itssafening activity is described in The Pesticide Manual, FourteenthEdition, 2006. Dichlormid is used as a safener for maize and sorghum.

Dicyclonon (BAS 145 138H) is the common name for(RS)-1-dichloroacetyl-3,3,8a-trimethylperhydropyrrolo[1,2]pyrimidin-6-one.Its safening activity is described in Pesticide Biochemistry andPhysiology 1992, 42, 128-139. Dicyclonon (BAS 145 138H) is used as asafener for maize.

Fenchlorazole is the common name for1-(2,4-dichlorophenyl)-5-(trichloromethyl)-1H-1,2,4-triazole-3-carboxylicacid. Its safening activity is described in The Pesticide Manual,Fourteenth Edition, 2006. Fenchlorazole is used as a safener in wheat,rye and triticale.

Fenclorim is the common name for 4,6-dichloro-2-phenylpyrimidine. Itssafening activity is described in The Pesticide Manual, FourteenthEdition, 2006. Fenclorim is used as a safener in direct-seeded rice.

Fluxofenim is the common name for1-(4-chlorophenyl)-2,2,2-trifluoroethanoneO-(1,3-dioxolan-2-ylmethyl)oxime. Its safening activity is described inThe Pesticide Manual, Fourteenth Edition, 2006. Fluxofenim is used as asafener in sorghum.

Furilazole (MON 13900) is the common name for3-(dichloroacetyl)-5-(2-furanyl)-2,2-dimethyloxazolidine. Its safeningactivity is described in The Pesticide Manual, Fourteenth Edition, 2006.Furilazole (MON 13900) is used as a safener in maize.

Isoxadifen-ethyl is the common name for ethyl4,5-dihydro-5,5-diphenyl-3-isoxazolecarboxylate. Its safening activityis described in The Pesticide Manual, Fourteenth Edition, 2006.Isoxadifen is used as a safener in maize.

Glyphosate is the common name for N-(phosphonomethyl)glycine. Itsherbicidal activity is described in The Pesticide Manual, FourteenthEdition, 2006. Glyphosate controls a wide range of annual and perennial,broadleaf and grass weeds.

Mefenpyr is the common name for1-(2,4-dichlorophenyl)-4,5-dihydro-5-methyl-1H-pyrazole-3,5-dicarboxylicacid. Its safening activity is described in The Pesticide Manual,Fourteenth Edition, 2006. Mefenpyr is used as a safener in wheat, rye,triticale and barley.

Naphthalic anhydride is the common name for1H,3H-naphtho[1,8-cd]pyran-1,3-dione. Its safening activity is describedin The Pesticide Manual, Eighth Edition, 1987. Naphthalic anhydride isused as a safener in maize and sorghum.

Oxabetrinil is the common name forα-[(1,3-dioxolan-2-yl)methoxyimino]benzene-acetonitrile. Its safeningactivity is described in The Pesticide Manual, Fourteenth Edition, 2006.Oxabetrinil is used as a safener in sorghum.

The term herbicide is used herein to mean an active ingredient thatkills, controls or otherwise adversely modifies the growth of plants. Anherbicidally effective or vegetation controlling amount is an amount ofactive ingredient which causes an adversely modifying effect andincludes deviations from natural development, killing, regulation,desiccation, retardation, and the like. The terms plants and vegetationinclude germinant seeds, emerging seedlings and established vegetation.The term safener, as used herein, refers to a compound that selectivelyprotects crop plants from herbicide damage without significantlyreducing activity in target weed species.

Herbicidal activity is exhibited by the compounds when they are applieddirectly to the plant or to the locus of the plant via foliar, soil, orwater application at any stage of growth or before planting oremergence. The effect observed depends upon the plant species to becontrolled, the stage of growth of the plant, the application parametersof dilution and spray drop size, the particle size of solid components,the environmental conditions at the time of use, the specific compoundemployed, the specific adjuvants and carriers employed, the soil type,and the like, as well as the amount of chemical applied. These and otherfactors can be adjusted as is known in the art to promote non-selectiveor selective herbicidal action. Generally, it is preferred to apply thecomposition of the present invention postemergence to relativelyimmature undesirable vegetation to achieve the maximum control of weeds.

Cultivated plants which are to be protected from the adverse effect ofundesirable plant growth may be damaged to a certain degree when aneffective dose of herbicides is used. Safening means preventing theadverse effect of an herbicide on the cultivated plants, i.e.,protecting the cultivated plants without, at the same time, noticeablyinfluencing the herbicidal action on weeds to be combated.

In the composition of this invention, the weight ratio of the safener tothe pyridinecarboxylate of formula (I) at which the herbicidal effect onthe cultivated plant is safened lies within the range of between about16:1 and about 1:32. Preferably, the weight ratio of the safener to thepyridinecarboxylate of formula (I) at which the herbicidal effect on thecultivated plant is safened lies within the range of between about 4:1and about 1:8.

The rate at which the safened composition is applied will depend uponthe particular type of weed to be controlled, the degree of controlrequired, and the timing and method of application. In general, thecomposition of the invention can be applied at an application rate ofbetween about 4 grams per hectare (g/ha) and about 1200 g/ha based onthe total amount of pyridinecarboxylate of formula (I) and safener inthe composition.

The pyridinecarboxylate of formula (I) and the safener of the presentinvention can be applied either separately or together as part of amultipart herbicidal system.

The herbicide-safener mixture of the present invention can be applied inconjunction with one or more other herbicides to control a wider varietyof undesirable vegetation. When used in conjunction with otherherbicides, the composition can be formulated with the other herbicideor herbicides, tank mixed with the other herbicide or herbicides orapplied sequentially with the other herbicide or herbicides. Some of theherbicides that can be employed in conjunction with the safenedcomposition of the present invention include: 2,4-D esters and amines,acetochlor, acifluorfen, aclonifen, AE0172747, alachlor,aminocyclopyrachlor, amidosulfuron, aminotriazole, ammonium thiocyanate,anilifos, atrazine, AVH 301, azimsulfuron, benfuresate,bensulfuron-methyl, bentazone, benthiocarb, benzobicyclon, bifenox,bispyribac-sodium, bromacil, bromoxynil, butachlor, butafenacil,butralin, cafenstrole, carbetamide, carfentrazone-ethyl, chlorflurenol,chlorimuron, chlorpropham, cinosulfuron, clethodim, clomazone,clopyralid, cloransulam-methyl, cyclosulfamuron, cycloxydim,cyhalofop-butyl, dicamba, dichlobenil, dichlorprop-P, diclosulam,diflufenican, diflufenzopyr, dimethenamid, dimethenamid-p, diquat,dithiopyr, diuron, EK2612, EPTC, esprocarb, ET-751, ethoxysulfuron,ethbenzanid, F7967, fenoxaprop, fenoxaprop-ethyl, fentrazamide,flazasulfuron, florasulam, fluazifop, fluazifop-P-butyl,flucetosulfuron, flufenacet, flufenpyr-ethyl, flumetsulam,flumiclorac-pentyl, flumioxazin, fluometuron, flupyrsulfuron,fluoroxypyr, fomesafen, foramsulfuron, fumiclorac, glufosinate,glufosinate-ammonium, glyphosate, halosulfuron, haloxyfop-methyl,haloxyfop-R, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin,imazethapyr, imazosulfuron, indanofan, iodosulfuron, ioxynil, IR 5790,isoproturon, isoxaben, isoxaflutole, KUH-021, lactofen, linuron, MCPA,MCPA ester & amine, mecoprop-P, mefenacet, mesosulfuron, mesotrione,metamifop, metolachlor, metosulam, metribuzin, metsulfuron, molinate,MSMA, napropamide, nicosulfuron, norflurazon, OK-9701, orthosulfamuron,oryzalin, oxadiargyl, oxadiazon, oxazichlomefone, oxyfluorfen, paraquat,pendimethalin, penoxsulam, pentoxazone, pethoxamid, picloram,picolinafen, piperophos, pretilachlor, profoxydim, propachlor, propanil,propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyrasulfotole,pyrazogyl, pyrazosulfuron, pyribenzoxim, pyriftalid, pyriminobac-methyl,primisulfuron, pyroxsulam, quinclorac, quizalofop-ethyl-D, S-3252,saflufenacil, sethoxydim, simazine, SL-0401, SL-0402, s-metolachlor,sulcotrione, sulfentrazone, sulfosate, tebuthiuron, terbacil, TH-547,thiazopyr, thiobencarb, triclopyr, triclopyr esters and amine,trifluralin and tritosulfuron.

The safened composition of the present invention can, further, be usedin conjunction with glyphosate, glufosinate, dicamba, imidazolinones or2,4-D on glyphosate-tolerant, glufosinate-tolerant, dicamba-tolerant,imidazolinone-tolerant or 2,4-D-tolerant crops. It is generallypreferred to use the herbicide-safener mixture of the present inventionin combination with herbicides that are selective for the crop beingtreated and which complement the spectrum of weeds controlled by thesecompounds at the application rate employed. It is further generallypreferred to apply the safened composition of the present invention andother complementary herbicides at the same time, either as a combinationformulation or as a tank mix.

In practice, it is preferable to use the safened composition of thepresent invention in mixtures containing an herbicidally effectiveamount of the herbicidal components along with at least oneagriculturally acceptable adjuvant or carrier. Suitable adjuvants orcarriers should not be phytotoxic to valuable crops, particularly at theconcentrations employed in applying the compositions for selective weedcontrol in the presence of crops, and should not react chemically withherbicidal components or other composition ingredients. Such mixturescan be designed for application directly to weeds or their locus or canbe concentrates or formulations that are normally diluted withadditional carriers and adjuvants before application. They can besolids, such as, for example, dusts, granules, water dispersiblegranules, or wettable powders, or liquids, such as, for example,emulsifiable concentrates, solutions, emulsions or suspensions.

Suitable agricultural adjuvants and carriers that are useful inpreparing the herbicidal mixtures of the invention are well known tothose skilled in the art. Some of these adjuvants include, but are notlimited to, crop oil concentrate (mineral oil (85%)+emulsifiers (15%));nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternary ammoniumsalt; blend of petroleum hydrocarbon, alkyl esters, organic acid, andanionic surfactant; C₉-C₁₁ alkylpolyglycoside; phosphated alcoholethoxylate; natural primary alcohol (C₁₂-C₁₆) ethoxylate;di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap;nonylphenol ethoxylate+urea ammonium nitrate; emulsified methylated seedoil; tridecyl alcohol (synthetic) ethoxylate (8EO); tallow amineethoxylate (15 EO); PEG(400) dioleate-99.

Liquid carriers that can be employed include water, toluene, xylene,petroleum naphtha, crop oil, acetone, methyl ethyl ketone,cyclohexanone, trichloroethylene, perchloroethylene, ethyl acetate, amylacetate, butyl acetate, propylene glycol monomethyl ether and diethyleneglycol monomethyl ether, methyl alcohol, ethyl alcohol, isopropylalcohol, amyl alcohol, ethylene glycol, propylene glycol, glycerine,N-methyl-2-pyrrolidinone, N,N-dimethyl alkylamides, dimethyl sulfoxide,liquid fertilizers and the like. Water is generally the carrier ofchoice for the dilution of concentrates.

Suitable solid carriers include talc, pyrophyllite clay, silica,attapulgus clay, kaolin clay, kieselguhr, chalk, diatomaceous earth,lime, calcium carbonate, bentonite clay, Fuller's earth, cotton seedhulls, wheat flour, soybean flour, pumice, wood flour, walnut shellflour, lignin, and the like.

It is usually desirable to incorporate one or more surface-active agentsinto the compositions of the present invention. Such surface-activeagents are advantageously employed in both solid and liquidcompositions, especially those designed to be diluted with carrierbefore application. The surface-active agents can be anionic, cationicor nonionic in character and can be employed as emulsifying agents,wetting agents, suspending agents, or for other purposes. Surfactantsconventionally used in the art of formulation and which may also be usedin the present formulations are described, inter alia, in “McCutcheon'sDetergents and Emulsifiers Annual,” MC Publishing Corp., Ridgewood,N.J., 1998 and in “Encyclopedia of Surfactants,” Vol. I-III, ChemicalPublishing Co., New York, 1980-81. Typical surface-active agents includesalts of alkyl sulfates, such as diethanolammonium lauryl sulfate;alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate;alkylphenol-alkylene oxide addition products, such as nonylphenol-C₁₈ethoxylate; alcohol-alkylene oxide addition products, such as tridecylalcohol-C₁₆ ethoxylate; soaps, such as sodium stearate;alkylnaphthalene-sulfonate salts, such as sodiumdibutyl-naphthalenesulfonate; dialkyl esters of sulfosuccinate salts,such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such assorbitol oleate; quaternary amines, such as lauryl trimethylammoniumchloride; polyethylene glycol esters of fatty acids, such aspolyethylene glycol stearate; block copolymers of ethylene oxide andpropylene oxide; salts of mono and dialkyl phosphate esters; vegetableoils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflowerseed oil, coconut oil, corn oil, cotton seed oil, linseed oil, palm oil,peanut oil, safflower oil, sesame oil, tung oil and the like; and estersof the above vegetable oils.

Other additives commonly used in agricultural compositions includecompatibilizing agents, antifoam agents, sequestering agents,neutralizing agents and buffers, corrosion inhibitors, dyes, odorants,spreading agents, penetration aids, sticking agents, dispersing agents,thickening agents, freezing point depressants, antimicrobial agents, andthe like. The compositions may also contain other compatible components,for example, other herbicides, plant growth regulants, fungicides,insecticides, and the like and can be formulated with liquid fertilizersor solid, particulate fertilizer carriers such as ammonium nitrate, ureaand the like.

The concentration of the active ingredients in the herbicide-safenermixture of the present invention is generally from 0.001 to 98 percentby weight. Concentrations from 0.01 to 90 percent by weight are oftenemployed. In compositions designed to be employed as concentrates, theactive ingredients are generally present in a concentration from 5 to 98weight percent, preferably 10 to 90 weight percent. Such compositionsare typically diluted with an inert carrier, such as water, beforeapplication. The diluted compositions usually applied to weeds or thelocus of weeds generally contain 0.0001 to 1 weight percent activeingredient and preferably contain 0.001 to 0.05 weight percent.

The present compositions can be applied to weeds or their locus by theuse of conventional ground or aerial dusters, sprayers, and granuleapplicators, or irrigation water, and by other conventional means knownto those skilled in the art.

The following examples illustrate the present invention.

Evaluation of Postemergence Herbicidal Safening in Cereal Crops

Seeds of the desired test plant species were planted in Sun GroMetroMix® 306 planting mixture, which typically has a pH of 6.0 to 6.8and an organic matter content of about 30 percent, in plastic pots witha surface area of 103.2 square centimeters (cm²). When required toensure good germination and healthy plants, a fungicide treatment and/orother chemical or physical treatment was applied. The plants were grownfor 7-36 days (d) in a greenhouse with an approximate 14-hour (h)photoperiod which was maintained at about 18° C. during the day and 17°C. during the night. Nutrients and water were added on a regular basisand supplemental lighting was provided with overhead metal halide1000-Watt lamps as necessary. The plants were employed for testing whenthey reached the second or third true leaf stage.

Weighed amounts of esters (methyl) or salts (TEA [triethylammonium], K[potassium]) of4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylicacid (Compound 1) were dissolved in a volume of 97:3 volume/volume (v/v)acetone/dimethylsulfoxide (DMSO) to obtain stock solutions. If theexperimental compound did not dissolve readily, the mixture was warmedand/or sonicated. The concentrated stock solutions were diluted with anaqueous mixture of 1.5% v/v of Agri-dex crop oil concentrate to providethe appropriate application rates. Compound requirements are based upona 12 mL application volume at a rate of 187 liters per hectare (L/ha).Stocks solutions of the safeners were prepared following the sameprocedure. Spray solutions of the safeners and experimental compoundmixtures were prepared by adding the stock solutions to the appropriateamount of dilution solution to form a 12 mL spray solution with activeingredients in two-way combinations. Formulated compounds were appliedto the plant material with an overhead Mandel track sprayer equippedwith 8002E nozzles calibrated to deliver 187 L/ha over an applicationarea of 0.503 square meters (m²) at a spray height of 18 inches (43centimeters (cm)) above average plant canopy. Control plants weresprayed in the same manner with the solvent blank.

The treated plants and control plants were placed in a greenhouse asdescribed above and watered by sub-irrigation to prevent wash-off of thetest compounds. After 20-22 d, the condition of the test plants ascompared with that of the control plants was determined visually andscored on a scale of 0 to 100 percent where 0 corresponds to no injuryand 100 corresponds to complete kill.

Colby's equation was used to determine the herbicidal effects expectedfrom the mixtures (Colby, S. R. Calculation of the synergistic andantagonistic response of herbicide combinations. Weeds 1967, 15,20-22.).

The following equation was used to calculate the expected activity ofmixtures containing two active ingredients, A and B:Expected=A+B−(A×B/100)

A=observed efficacy of active ingredient A at the same concentration asused in the mixture.

B=observed efficacy of active ingredient B at the same concentration asused in the mixture.

Some of the compounds tested, application rates employed, plant speciestested, and results are given in Table 1 through Table 22.

TABLE 1 Safening Activity of Herbicidal Compositions on Wheat and BarleyApplication Rate (g/ha) Compound Herbicide:Safener TRZAS HORVS GALAPKCHSC LAMPU MATCH 1 TEA salt AD67 Ratio Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex ObEx 140 0 26 — 16 — 100 — 94 — 99 — 80 — 0 140 0 — 0 — 0 — — — — 0 70 0 —0 — 0 — — — — 0 35 0 — 0 — 0 — — — — 0 17.5 0 — 0 — 0 — — — — 140 1401:1 10 26 6 16 100 100 83 94 100 99 80 80 140 70 2:1 11 26 9 16 100 10075 94 99 99 63 80 140 35 4:1 10 26 0 16 100 100 95 94 99 99 73 80Application Rate (g/ha) Compound Herbicide:Safener PAPRH POLCO SASKRSTEME VERPE VIOTR 1 TEA salt AD67 Ratio Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex ObEx 140 0 100 — 100 — 88 — 94 — 85 — 69 — 0 140 0 — 0 — 0 — 0 — 0 — 0 — 070 0 — 0 — 0 — 0 — 0 — 0 — 0 35 0 — 0 — 0 — 0 — 0 — 0 — 0 17.5 0 — 0 — 0— 0 — 0 — 0 — 140 140 1:1 100 100 100 100 85 88 88 94 89 85 58 69 140 702:1 100 100 93 100 83 88 100 94 89 85 68 69 140 35 4:1 100 100 88 100 8588 100 94 88 85 65 69

TABLE 2 Safening Activity of Herbicidal Compositions on Wheat and BarleyApplication Rate (g/ha) Compound Herbicide:Safener TRZAS HORVS GALAPKCHSC LAMPU MATCH 1 TEA salt Benoxacor Ratio Ob Ex Ob Ex Ob Ex Ob Ex ObEx Ob Ex 140 0 26 — 16 — 100 — 94 — 99 — 80 — 0 140 0 — 0 — 0 — — — — 070 0 — 0 — 0 — — — — 0 35 0 — 0 — 0 — — — — 0 17.5 0 — 0 — 0 — — — — 140140 1:1 7 26 5 16 100 100 91 94 100 99 78 80 140 70 2:1 14 26 7 16 100100 96 94 100 99 90 80 140 35 4:1 20 26 0 16 100 100 96 94 100 99 80 80Application Rate (g/ha) Compound Herbicide:Safener PAPRH POLCO SASKRSTEME VERPE VIOTR 1 TEA salt Benoxacor Ratio Ob Ex Ob Ex Ob Ex Ob Ex ObEx Ob Ex 140 0 100 — 100 — 88 — 94 — 85 — 69 — 0 140 0 — 0 — 0 — 0 — 0 —0 — 0 70 0 — 0 — 0 — 0 — 0 — 0 — 0 35 0 — 0 — 0 — 0 — 0 — 0 — 0 17.5 0 —0 — 0 — 0 — 0 — 0 — 140 140 1:1 100 100 98 100 85 88 99 94 85 85 78 69140 70 2:1 100 100 98 100 85 88 95 94 80 85 65 69 140 35 4:1 100 100 98100 85 88 99 94 83 85 65 69

TABLE 3 Safening Activity of Herbicidal Compositions on Wheat and BarleyApplication Rate (g/ha) Compound Herbicide:Safener TRZAS HORVS GALAPKCHSC LAMPU MATCH 1 TEA salt 2-CBSU Ratio Ob Ex Ob Ex Ob Ex Ob Ex Ob ExOb Ex 140 0 26 — 16 — 100 — 94 — 99 — 80 — 0 140 0 — 0 — 0 — — — — 0 700 — 0 — 0 — — — — 0 35 0 — 0 — 0 — — — — 0 17.5 0 — 0 — 0 — — — — 140140 1:1 5 26 4 16 100 100 85 94 100 99 78 80 140 70 2:1 11 26 10 16 100100 95 94 100 99 85 80 140 35 4:1 10 26 0 16 100 100 90 94 100 99 83 80Application Rate (g/ha) Compound Herbicide:Safener PAPRH POLCO SASKRSTEME VERPE VIOTR 1 TEA salt 2-CBSU Ratio Ob Ex Ob Ex Ob Ex Ob Ex Ob ExOb Ex 140 0 100 — 100 — 88 — 94 — 85 — 69 — 0 140 0 — 0 — 0 — 0 — 0 — 0— 0 70 0 — 0 — 0 — 0 — 0 — 0 — 0 35 0 — 0 — 0 — 0 — 0 — 0 — 0 17.5 0 — 0— 0 — 0 — 0 — 0 — 140 140 1:1 100 100 97 100 89 88 98 94 85 85 50 69 14070 2:1 100 100 93 100 88 88 98 94 88 85 70 69 140 35 4:1 100 100 96 10085 88 85 94 92 85 65 69

TABLE 4 Safening Activity of Herbicidal Compositions on Wheat and BarleyApplication Rate (g/ha) Compound Herbicide:Safener TRZAS HORVS GALAPKCHSC LAMPU MATCH 1 TEA salt Dichlormid Ratio Ob Ex Ob Ex Ob Ex Ob Ex ObEx Ob Ex 140 0 26 — 16 — 100 — 94 — 99 — 80 — 0 140 0 — 0 — 0 — 0 — 0 —0 — 0 70 0 — 0 — 0 — 0 — 0 — 0 — 0 35 0 — 0 — 0 — 0 — 0 — 0 — 0 17.5 0 —0 — 0 — 0 — 0 — 0 — 140 140 1:1 15 26 20 16 100 100 100 94 100 99 73 80140 70 2:1 6 26 15 16 100 100 85 94 100 99 84 80 140 35 4:1 7 26 0 16100 100 83 94 100 99 73 80 Application Rate (g/ha) CompoundHerbicide:Safener PAPRH POLCO SASKR STEME VERPE VIOTR 1 TEA saltDichlormid Ratio Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex 140 0 100 — 100 —88 — 94 — 85 — 69 — 0 140 0 — 0 — 0 — 0 — 0 — 0 — 0 70 0 — 0 — 0 — 0 — 0— 0 — 0 35 0 — 0 — 0 — 0 — 0 — 0 — 0 17.5 0 — 0 — 0 — 0 — 0 — 0 — 140140 1:1 100 100 98 100 90 88 98 94 90 85 68 69 140 70 2:1 100 100 99 10080 84 90 94 93 85 65 69 140 35 4:1 100 100 98 100 95 85 95 94 90 85 4869

TABLE 5 Safening Activity of Herbicidal Compositions on Wheat and BarleyApplication Rate (g/ha) Compound 1 Herbicide:Safener TRZAS HORVS GALAPKCHSC LAMPU MATCH TEA salt Dicyclonon Ratio Ob Ex Ob Ex Ob Ex Ob Ex ObEx Ob Ex 140 0 26 — 16 — 100 — 94 — 99 — 80 — 0 140 0 — 0 — 0 — — — — 070 0 — 0 — 0 — — — — 0 35 0 — 0 — 0 — — — — 0 17.5 0 — 0 — 0 — — — — 140140 1:1 9 26 4 16 100 100 99 94 100 99 85 80 140 70 2:1 4 26 8 16 100100 80 94 100 99 83 80 140 35 4:1 0 26 0 16 100 100 80 94 100 99 75 80Application Rate (g/ha) Compound 1 Herbicide:Safener PAPRH POLCO SASKRSTEME VERPE VIOTR TEA salt Dicyclonon Ratio Ob Ex Ob Ex Ob Ex Ob Ex ObEx Ob Ex 140 0 100 — 100 — 88 — 94 — 85 — 69 — 0 140 0 — 0 — 0 — 0 — 0 —0 — 0 70 0 — 0 — 0 — 0 — 0 — 0 — 0 35 0 — 0 — 0 — 0 — 0 — 0 — 0 17.5 0 —0 — 0 — 0 — 0 — 0 — 140 140 1:1 100 100 99 100 85 88 79 94 87 85 70 69140 70 2:1 100 100 100 100 88 88 99 94 88 85 70 69 140 35 4:1 100 100 99100 86 88 100 94 85 85 50 69

TABLE 6 Safening Activity of Herbicidal Compositions on Wheat and BarleyApplication Rate (g/ha) Compound Fenchlorazole- Herbicide:Safener TRZASHORVS GALAP KCHSC LAMPU MATCH 1 TEA salt ethyl Ratio Ob Ex Ob Ex Ob ExOb Ex Ob Ex Ob Ex 140 0 26 — 16 — 100 — 94 — 99 — 80 — 0 140 0 — 0 — 0 —— — — 0 70 0 — 0 — 0 — — — — 0 35 0 — 0 — 0 — — — — 0 17.5 0 — 0 — 0 — —— — 140 140 1:1 0 26 0 16 100 100 98 94 100 99 65 80 140 70 2:1 0 26 016 100 100 99 94 100 99 68 80 140 35 4:1 0 26 0 16 100 100 94 94 100 9978 80 Application Rate (g/ha) Compound Fenchlorazole- Herbicide:SafenerPAPRH POLCO SASKR STEME VERPE VIOTR 1 TEA salt ethyl Ratio Ob Ex Ob ExOb Ex Ob Ex Ob Ex Ob Ex 140 0 100 — 100 — 88 — 94 — 85 — 69 — 0 140 0 —0 — 0 — 0 — 0 — 0 — 0 70 0 — 0 — 0 — 0 — 0 — 0 — 0 35 0 — 0 — 0 — 0 — 0— 0 — 0 17.5 0 — 0 — 0 — 0 — 0 — 0 — 140 140 1:1 100 100 99 100 88 88 9994 88 85 73 69 140 70 2:1 100 100 94 100 89 88 98 94 88 85 75 69 140 354:1 100 100 83 100 88 88 80 94 89 85 75 69

TABLE 7 Safening Activity of Herbicidal Compositions on Wheat and BarleyApplication Rate (g/ha) Compound 1 Herbicide:Safener TRZAS HORVS GALAPKCHSC LAMPU MATCH TEA salt Fenclorim Ratio Ob Ex Ob Ex Ob Ex Ob Ex Ob ExOb Ex 140 0 26 — 16 — 100 — 94 — 99 — 80 — 0 140 0 — 0 — 0 — 0 — 0 — 0 —0 70 0 — 0 — 0 — 0 — 0 — 0 — 0 35 0 — 0 — 0 — 0 — 0 — 0 — 0 17.5 0 — 0 —0 — 0 — 0 — 0 — 140 140 1:1 6 26 4 16 100 100 95 94 100 99 78 80 140 702:1 7 26 8 16 100 100 93 94 100 99 77 80 140 35 4:1 8 26 5 16 100 100 8994 100 99 60 80 Application Rate (g/ha) Compound 1 Herbicide:SafenerPAPRH POLCO SASKR STEME VERPE VIOTR TEA salt Fenclorim Ratio Ob Ex Ob ExOb Ex Ob Ex Ob Ex Ob Ex 140 0 100 — 100 — 88 — 94 — 85 — 69 — 0 140 0 —0 — 0 — 0 — 0 — 0 — 0 70 0 — 0 — 0 — 0 — 0 — 0 — 0 35 0 — 0 — 0 — 0 — 0— 0 — 0 17.5 0 — 0 — 0 — 0 — 0 — 0 — 140 140 1:1 100 100 99 100 85 88 9494 93 85 65 69 140 70 2:1 100 100 99 100 89 88 88 94 90 85 68 69 140 354:1 100 100 96 100 88 88 93 94 90 85 65 69

TABLE 8 Safening Activity of Herbicidal Compositions on Wheat and BarleyApplication Rate (g/ha) Compound 1 Herbicide:Safener TRZAS HORVS GALAPKCHSC LAMPU MATCH TEA salt Fluxofenim Ratio Ob Ex Ob Ex Ob Ex Ob Ex ObEx Ob Ex 140 0 26 — 16 — 100 — 94 — 99 — 80 — 0 140 0 — 0 — 0 — — — — 070 0 — 0 — 0 — — — — 0 35 0 — 0 — 0 — — — — 0 17.5 0 — 0 — 0 — — — — 140140 1:1 0 26 11 16 100 100 89 94 98 99 80 80 140 70 2:1 1 26 13 16 100100 89 94 100 99 78 80 140 35 4:1 0 26 0 16 100 100 90 94 100 99 84 80Application Rate (g/ha) Compound 1 Herbicide:Safener PAPRH POLCO SASKRSTEME VERPE VIOTR TEA salt Fluxofenim Ratio Ob Ex Ob Ex Ob Ex Ob Ex ObEx Ob Ex 140 0 100 — 100 — 88 — 94 — 85 — 69 — 0 140 0 — 0 — 0 — 0 — 0 —0 — 0 70 0 — 0 — 0 — 0 — 0 — 0 — 0 35 0 — 0 — 0 — 0 — 0 — 0 — 0 17.5 0 —0 — 0 — 0 — 0 — 0 — 140 140 1:1 100 100 100 100 89 88 99 94 89 85 68 69140 70 2:1 100 100 93 100 89 88 100 94 92 85 68 69 140 35 4:1 100 100100 100 89 88 100 94 89 85 68 69

TABLE 9 Safening Activity of Herbicidal Compositions on Wheat and BarleyApplication Rate (g/ha) Furilazole Compound (MON Herbicide:Safener TRZASHORVS GALAP KCHSC LAMPU MATCH 1 TEA salt 13900) Ratio Ob Ex Ob Ex Ob ExOb Ex Ob Ex Ob Ex 140 0 26 16 100 94 99 80 0 140 0 0 0 0 0 0 0 70 0 0 00 0 0 0 35 0 0 0 0 0 0 0 17.5 0 0 0 0 0 0 140 140 1:1 6 26 4 16 100 10086 94 100 99 70 80 140 70 2:1 8 26 9 16 100 100 89 94 100 99 93 80 14035 4:1 5 26 7 16 100 100 87 94 100 99 85 80 140 17.5 8:1 2 26 13 16 100100 85 94 100 99 80 Application Rate (g/ha) Furilazole Compound (MONHerbicide:Safener PAPRH POLCO SASKR STEME VERPE VIOTR 1 TEA salt 13900)Ratio Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex 140 0 100 100 88 94 85 69 0140 0 0 0 0 0 0 0 70 0 0 0 0 0 0 0 35 0 0 0 0 0 0 0 17.5 0 0 0 0 0 0 140140 1:1 100 100 94 100 92 88 85 94 78 85 73 69 140 70 2:1 100 100 97 10090 88 90 94 82 85 73 69 140 35 4:1 100 100 93 100 91 88 83 94 83 85 7369 140 17.5 8:1 100 100 95 100 90 88 83 94 80 85 75 69

TABLE 10 Safening Activity of Herbicidal Compositions on Wheat andBarley Application Rate (g/ha) Compound 1 Mefenpyr- Herbicide:SafenerTRZAS HORVS GALAP KCHSC LAMPU MATCH TEA salt diethyl Ratio Ob Ex Ob ExOb Ex Ob Ex Ob Ex Ob Ex 140 0 26 — 16 — 100 — 94 — 99 — 80 — 0 140 0 — 0— 0 — — — — 0 70 0 — 0 — 0 — — — — 0 35 0 — 0 — 0 — — — — 0 17.5 0 — 0 —0 — — — — 140 140 1:1 1 26 3 16 100 100 75 94 100 99 70 80 140 70 2:1 026 3 16 100 100 75 94 100 99 85 80 140 35 4:1 2 26 4 16 100 100 70 94100 99 80 80 Application Rate (g/ha) Compound 1 Mefenpyr-Herbicide:Safener PAPRH POLCO SASKR STEME VERPE VIOTR TEA salt diethylRatio Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex 140 0 100 — 100 — 88 — 94 — 85— 69 — 0 140 0 — 0 — 0 — 0 — 0 — 0 — 0 70 0 — 0 — 0 — 0 — 0 — 0 — 0 35 0— 0 — 0 — 0 — 0 — 0 — 0 17.5 0 — 0 — 0 — 0 — 0 — 0 — 140 140 1:1 100 10098 100 94 88 87 94 88 85 75 69 140 70 2:1 100 100 95 100 90 88 88 94 8885 75 69 140 35 4:1 100 100 90 100 88 88 88 94 83 85 70 69

TABLE 11 Safening Activity of Herbicidal Compositions on Wheat andBarley Application Rate (g/ha) Compound Naphthalic Herbicide:SafenerTRZAS HORVS GALAP KCHSC LAMPU MATCH 1 TEA salt anhydride Ratio Ob Ex ObEx Ob Ex Ob Ex Ob Ex Ob Ex 140 0 26 — 16 — 100 — 94 — 99 — 80 — 0 140 0— 0 — 0 — — — — 0 70 0 — 0 — 0 — — — — 0 35 0 — 0 — 0 — — — — 0 17.5 0 —0 — 0 — — — — 140 140 1:1 13 26 8 16 100 100 91 94 100 99 93 80 140 702:1 16 26 11 16 100 100 93 94 100 99 87 80 140 35 4:1 10 26 4 16 100 10094 94 100 99 75 80 Application Rate (g/ha) Compound NaphthalicHerbicide:Safener PAPRH POLCO SASKR STEME VERPE VIOTR 1 TEA saltanhydride Ratio Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex 140 0 100 — 100 — 88— 94 — 85 — 69 — 0 140 0 — 0 — 0 — 0 — 0 — 0 — 0 70 0 — 0 — 0 — 0 — 0 —0 — 0 35 0 — 0 — 0 — 0 — 0 — 0 — 0 17.5 0 — 0 — 0 — 0 — 0 — 0 — 140 1401:1 100 100 99 100 88 88 94 94 87 85 78 69 140 70 2:1 100 100 100 100 8988 95 94 85 85 75 69 140 35 4:1 100 100 98 100 87 88 98 94 88 85 70 69

TABLE 12 Safening Activity of Herbicidal Compositions on Wheat andBarley Application Rate (g/ha) Compound 1 Herbicide:Safener TRZAS HORVSGALAP KCHSC LAMPU MATCH TEA salt Oxabetrinil Ratio Ob Ex Ob Ex Ob Ex ObEx Ob Ex Ob Ex 140 0 26 — 16 — 100 — 94 — 99 — 80 — 0 140 0 — 0 — 0 — 0— 0 — 0 — 0 70 0 — 0 — 0 — 0 — 0 — 0 — 0 35 0 — 0 — 0 — 0 — 0 — 0 — 017.5 0 — 0 — 0 — 0 — 0 — 0 — 140 140 1:1 20 26 16 16 100 100 92 94 10099 93 80 140 70 2:1 21 26 18 16 100 100 90 94 100 99 87 80 140 35 4:1 1326 10 16 100 100 99 94 100 99 97 80 Application Rate (g/ha) Compound 1Herbicide:Safener PAPRH POLCO SASKR STEME VERPE VIOTR TEA saltOxabetrinil Ratio Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex 140 0 100 — 100 —88 — 94 — 85 — 69 — 0 140 0 — 0 — 0 — 0 — 0 — 0 — 0 70 0 — 0 — 0 — 0 — 0— 0 — 0 35 0 — 0 — 0 — 0 — 0 — 0 — 0 17.5 0 — 0 — 0 — 0 — 0 — 0 — 140140 1:1 100 100 98 100 94 88 100 94 92 85 73 69 140 70 2:1 100 100 97100 90 88 100 94 89 85 80 69 140 35 4:1 100 100 97 100 89 88 89 94 88 8573 69

TABLE 13 Safening Activity of Herbicidal Compositions on Wheat andBarley Application Rate (g/ha) Compound Herbicide:Safener TRZAS HORVSMATCH VIOTR 1 K salt Glyphosate Ratio Ob Ex Ob Ex Ob Ex Ob Ex 8.75 0 5 —1.7 — 50 — 20 — 17.5 0 8 — 3.3 — 62 — 48 — 35 0 27 — 6.7 — 57 — 42 — 052.5 48 — 13 — 28 — 52 — 8.75 52.5 1:6 37 51 12 15 55 64 75 61 7.5 52.51:7 37 53 10 16 58 73 77 75 35 52.5   1:1.5 45 62 12 19 75 69 83 72

TABLE 14 Safening Activity of Herbicidal Compositions on Wheat andBarley Application Rate (g/ha) Compound 1 Herbicide:Safener HORVW TRZDUTRZAW LAMPU PAPRH Methyl ester AD-67 Ratio Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex35 0 0 50 — 42 — 35 — 97 — 97 — 0 4.4 0 — 0 — 0 — 0 — 0 — 0 8.8 0 — 0 —0 — 0 — 0 — 0 17.5 0 — 0 — 0 — 0 — 0 — 0 35 0 — 0 — 0 — 0 — 0 — 35 351:1 30 50 22 42 12 35 97 97 95 97 35 17.5 2:1 13 50 20 42 13 35 100 97100 97 35 8.8 4:1 13 50 18 42 17 35 100 97 100 97 35 4.4 8:1 15 50 13 4213 35 100 97 100 97

TABLE 15 Safening Activity of Herbicidal Compositions on Wheat andBarley Application Rate (g/ha) Compound 1 Herbicide:Safener HORVW TRZDUTRZAW LAMPU PAPRH Methyl ester Benoxacor Ratio Ob Ex Ob Ex Ob Ex Ob ExOb Ex 35 0 0 50 — 42 — 35 — 97 — 97 — 0 4.4 0 — 0 — 0 — 0 — 0 — 0 8.8 0— 0 — 0 — 0 — 0 — 0 17.5 0 — 0 — 0 — 0 — 0 — 0 35 0 — 0 — 0 — 0 — 0 — 3535 1:1 15 50 18 42 15 35 100 97 100 97 35 17.5 2:1 15 50 17 42 18 35 10097 100 97 35 8.8 4:1 13 50 25 42 22 35 100 97 100 97 35 4.4 8:1 10 50 2042 20 35 100 97 100 97

TABLE 16 Safening Activity of Herbicidal Compositions on Wheat andBarley Application Rate (g/ha) Compound 1 2- Herbicide:Safener HORVWTRZDU TRZAW LAMPU PAPRH Methyl ester CBSU Ratio Ob Ex Ob Ex Ob Ex Ob ExOb Ex 35 0 0 50 — 42 — 35 — 97 — 97 — 0 4.4 0 — 0 — 0 — 0 — 0 — 0 8.8 0— 0 — 0 — 0 — 0 — 0 17.5 0 — 0 — 0 — 0 — 0 — 0 35 0 — 0 — 0 — 0 — 0 — 3535 1:1 12 50 22 42 13 35 100 97 100 97 35 17.5 2:1 15 50 22 42 20 35 40097 100 97 35 8.8 4:1 20 50 20 42 20 35 100 97 100 97 35 4.4 8:1 22 50 2542 25 35 100 97 100 97

TABLE 17 Safening Activity of Herbicidal Compositions on Wheat andBarley Application Rate (g/ha) Compound 1 Herbicide:Safener HORVW TRZDUTRZAW HORVS LAMPU PAPRH Methyl ester Daimuron Ratio Ob Ex Ob Ex Ob Ex ObEx Ob Ex Ob Ex 35 0 0 50 — 42 — 35 — 33 — 97 — 97 — 0 4.4 0 — 0 — 0 — 0— 0 — 0 — 0 8.8 0 — 0 — 0 — 0 — 0 — 0 — 0 17.5 0 — 0 — 0 — 0 — 0 — 0 — 035 0 — 0 — 0 — 0 — 0 — 0 — 35 35 1:1 3 50 7 42 10 35 18 33 100 97 95 9735 17.5 2:1 15 50 12 42 10 35 12 33 100 97 100 97 35 8.8 4:1 20 50 15 4210 35 12 33 100 97 100 97 35 4.4 8:1 20 50 15 42 15 35 15 33 100 97 10097

TABLE 18 Safening Activity of Herbicidal Compositions on Wheat andBarley Application Rate (g/ha) Compound 1 Herbicide:Safener HORVW TRZDUTRZAW HORVS LAMPU PAPRH Methyl ester Dichlormid Ratio Ob Ex Ob Ex Ob ExOb Ex Ob Ex Ob Ex 35 0 0 50 — 42 — 35 — 33 — 97 — 97 — 0 4.4 0 — 0 — 0 —0 — 0 — 0 — 0 8.8 0 — 0 — 0 — 0 — 0 — 0 — 0 17.5 0 — 0 — 0 — 0 — 0 — 0 —0 35 0 — 0 — 0 — 0 — 0 — 0 — 35 35 1:1 5 50 13 42 10 35 13 33 100 97 9897 35 17.5 2:1 8 50 13 42 17 35 15 33 100 97 100 97 35 8.8 4:1 10 50 1842 18 35 18 33 100 97 100 97 35 4.4 8:1 27 50 15 42 22 35 20 33 100 97100 97

TABLE 19 Safening Activity of Herbicidal Compositions on Wheat andBarley Application Rate (g/ha) Compound 1 Herbicide:Safener HORVW TRZDUTRZAW HORVS LAMPU PAPRH Methyl ester Dicyclonon Ratio Ob Ex Ob Ex Ob ExOb Ex Ob Ex Ob Ex 35 0 0 50 — 42 — 35 — 33 — 97 — 97 — 0 4.4 0 — 0 — 0 —0 — 0 — 0 — 0 8.8 0 — 0 — 0 — 0 — 0 — 0 — 0 17.5 0 — 0 — 0 — 0 — 0 — 0 —0 35 0 — 0 — 0 — 0 — 0 — 0 — 35 35 1:1 20 50 27 42 25 35 22 33 100 97100 97 35 17.5 2:1 15 50 23 42 22 35 25 33 100 97 100 97 35 8.8 4:1 1550 23 42 22 35 23 33 100 97 100 97 35 4.4 8:1 18 50 27 42 27 35 20 33100 97 100 97

TABLE 20 Safening Activity of Herbicidal Compositions on Wheat andBarley Application Rate (g/ha) Compound 1 Herbicide:Safener TRZAS HORVWTRZDU TRZAW HORVS LAMPU PAPRH Methyl ester Fenchlorazole Ratio Ob Ex ObEx Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex 35 0 0 50 — 50 — 42 — 35 — 33 — 97 — 97— 0 4.4 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 8.8 0 — 0 — 0 — 0 — 0 — 0 — 0 — 017.5 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 35 0 — 0 — 0 — 0 — 0 — 0 — 0 — 35 351:1 0 50 0 50 0 42 0 35 0 33 100 97 100 97 35 17.5 2:1 0 50 0 50 0 42 035 0 33 100 97 100 97 35 8.8 4:1 0 50 0 50 0 42 0 35 0 33 100 97 100 9735 4.4 8:1 0 50 0 50 0 42 0 35 0 33 100 97 100 97

TABLE 21 Safening Activity of Herbicidal Compositions on Wheat andBarley Application Rate (g/ha) Compound 1 Herbicide:Safener TRZAS HORVWTRZDU TRZAW HORVS LAMPU PAPRH Methyl ester Isoxadifen Ratio Ob Ex Ob ExOb Ex Ob Ex Ob Ex Ob Ex Ob Ex 35 0 0 50 — 50 — 42 — 35 — 33 — 97 — 97 —0 4.4 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 8.8 0 — 0 — 0 — 0 — 0 — 0 — 0 — 017.5 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 35 0 — 0 — 0 — 0 — 0 — 0 — 0 — 35 351:1 0 50 5 50 12 42 0 35 0 33 98 97 100 97 35 17.5 2:1 3.3 50 12 50 1742 3.3 35 5 33 98 97 100 97 35 8.8 4:1 33 50 37 50 32 42 13 35 15 33 9797 98 97 35 4.4 8:1 42 50 42 50 37 42 17 35 17 33 99 97 100 97

TABLE 22 Safening Activity of Herbicidal Compositions on Wheat andBarley Application Rate (g/ha) Compound 1 Mefenpyr- Herbicide:SafenerTRZAS HORVW TRZDU TRZAW HORVS LAMPU PAPRH Methyl ester diethyl Ratio ObEx Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex 35 0 0 50 — 50 — 42 — 35 — 33 —97 — 97 — 0 4.4 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 8.8 0 — 0 — 0 — 0 — 0 — 0— 0 — 0 17.5 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 35 0 — 0 — 0 — 0 — 0 — 0 — 0— 35 35 1:1 0 50 0 50 0 42 0 35 0 33 97 97 100 97 35 17.5 2:1 0 50 0 500 42 0 35 0 33 96 97 97 97 35 8.8 4:1 0 50 0 50 0 42 0 35 0 33 98 97 9897 35 4.4 8:1 0 50 0 50 0 42 0 35 0 33 98 97 100 97 TRZAS = Triticumaestivum (spring wheat) HORVS = Hordeum vulgare (spring barley) GALAP =Galium aparine (cleavers) KCHSC = Kochia scoparia (kochia) LAMPU =Lamium purpureum (purple deadnettle) MATCH = Matricaria chamomila(scented mayweed) Ob = Observed values g/ha = grams/hectareHerbicide:Safener Ratio = Ratio herbicide to safener PAPRH = Papaverrhoeas (corn poppy) POLCO = Polygonum convolvulus (wild buckwheat) SASKR= Salsola iberica (Russian thistle) STEME = Stellaria media (commonchickweed) VERPE = Veronica persica (bird's-eye speedwell) VIOTR = Violatricolor (wild pansy) Ex = Expected values

What is claimed is:
 1. A composition for protecting wheat and barleyfrom the harmful effects of a 6-(trisubstitutedphenyl)-4-amino-2-pyridinecarboxylate herbicide, comprising acombination of a 6-(trisubstituted phenyl)-4-amino-2-pyridinecarboxylateherbicide according to the formula (I):

wherein hal represents F, Cl or Br, and R represents methyl or ethyl,and its agriculturally acceptable salt, ester and amide derivatives, anda safener or a compatible herbicide capable of safening, selected fromthe group consisting of AD67, benoxacor, 2-CBSU, daimuron, dichlormid,dicyclonon, fenchlorazole-ethyl, fenclorim, fluxofenim, furilazole,isoxadifenethyl, mefenpyr-diethyl, naphthalic anhydride, oxabetrinil andmixtures thereof, wherein the weight ratio of the 6-(trisubstitutedphenyl)-4-amino-2-pyridinecarboxylate herbicide to the safener or thecompatible herbicide capable of safening in the combination is fromabout 2:1 to about 32:1; and wherein the combination exhibits anobserved safening effect on the 6-(trisubstitutedphenyl)-4-amino-2-pyridinecarboxylate herbicide that is greater than theexpected safening effect.
 2. The composition of claim 1 in which the6-(trisubstituted phenyl)-4-amino-2-pyridinecarboxylate herbicide is a4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylicacid derivative or a4-amino-3-chloro-6-(2,4-dichloro-3-methoxy-phenyl)-2-pyridinecarboxylicacid derivative.
 3. The composition of claim 1, wherein the herbicide offormula (I) is

or its methyl ester or triethylammonium salt.
 4. The composition ofclaim 1, wherein the herbicide of formula (I) is


5. The composition of claim 2, wherein the herbicide of formula (I) is

or its methyl ester or triethylammonium salt.
 6. The composition ofclaim 2, wherein the herbicide of formula (I) is


7. A method of protecting wheat and barley from the harmful effects of a6-(trisubstituted phenyl)-4-amino-2-pyridinecarboxylate herbicidecomprising the step of contacting the wheat and barley with, or applyingto the area under cultivation of wheat and barley a combination of a6-(trisubstituted phenyl)-4-amino-2-pyridinecarboxylate herbicideaccording to the formula (I):

wherein hal represents F, Cl or Br, and R represents methyl or ethyl,and its agriculturally acceptable salt, ester and amide derivatives, anda safener, or a compatible herbicide capable of safening, selected fromthe group consisting of AD67, benoxacor, 2-CBSU, daimuron, dichlormid,dicyclonon, fenchlorazole-ethyl, fenclorim, fluxofenim, furilazole,isoxadifenethyl, mefenpyr-diethyl, naphthalic anhydride, oxabetrinil andmixtures thereof wherein the weight ratio of the 6-(trisubstitutedphenyl)-4-amino-2-pyridinecarboxylate herbicide to the safener orcompatible herbicide capable of safening in the combination is fromabout 2:1 to about 32:1; and wherein the combination exhibits anobserved safening effect that is greater than the expected safeningeffect.
 8. The method of claim 7, wherein the herbicide of formula (I)is:

or its methyl ester or triethylammonium salt.
 9. The method of claim 7,wherein the herbicide of formula (I) is


10. The method of claim 7, wherein the wheat and barley is Triticumaestivum or Hordeum vulgare.
 11. A composition which is effective inprotecting wheat and barley from the harmful effects of a6-(trisubstituted phenyl)-4-amino-2-pyridinecarboxylate herbicide,comprising a combination of a 6-(trisubstitutedphenyl)-4-amino-2-pyridinecarboxylate herbicide according to the formula(I):

wherein hal represents F, Cl or Br, and R represents methyl or ethyl,and its agriculturally acceptable salt, ester and amide derivatives, anda 2-CBSU safener; wherein the ratio range of the formula (I) to thesafener is from about 2:1 to about 32:1, and wherein the combinationexhibits an observed safening effect that is greater than the expectedsafening effect.
 12. A method of applying the composition of claim 11for protecting wheat and barley which comprises contacting the wheat andbarley with, or applying to the area under cultivation of wheat andbarley, the composition.
 13. The composition of claim 11, wherein theweight ratio of the 6-(trisubstitutedphenyl)-4-amino-2-pyridinecarboxylate herbicide to 2-CBSU is from about16:1 to about 2:1.
 14. The composition of claim 11, wherein the weightratio of the 6-(trisubstituted phenyl)-4-amino-2-pyridinecarboxylateherbicide to 2-CBSU is from about 4:1 to about 2:1.
 15. The compositionof claim 11, wherein the weight ratio of the 6-(trisubstitutedphenyl)-4-amino-2-pyridinecarboxylate herbicide to 2-CBSU is from about1:1 to about 2:1.
 16. The composition of claim 11, wherein the weightratio of the 6-(trisubstituted phenyl)-4-amino-2-pyridinecarboxylateherbicide to 2-CBSU is from greater than 2:1 to about 8:1.
 17. Themethod of claim 12, wherein the weight ratio of the 6-(trisubstitutedphenyl)-4-amino-2-pyridinecarboxylate herbicide to 2-CBSU is from about16:1 to about 2:1.
 18. The method of claim 12, wherein the weight ratioof the 6-(trisubstituted phenyl)-4-amino-2-pyridinecarboxylate herbicideto 2-CBSU is from about 4:1 to about 2:1.
 19. The method of claim 12,wherein the weight ratio of the 6-(trisubstitutedphenyl)-4-amino-2-pyridinecarboxylate herbicide to 2-CBSU is from about2:1 to about 8:1.
 20. The method of claim 12, wherein the weight ratioof the 6-(trisubstituted phenyl)-4-amino-2-pyridinecarboxylate herbicideto 2-CBSU is from greater than 2:1 to about 8:1.